Hydrocarbon synthesis catalyst



United States Patent 2,729,664 HYDROQARBON SYNTHESIS CATALYST Isidor Kirshenbaum, Union, N. J., assignor to Essa Research and Engineering Company, a corporation of Delaware No Drawing. Continuation of application Serial No. 792,851, December 19, 1947. This application August 2, 1951, Serial No. 240,031

1 Claim. (Cl. 26li449.6)

This application is a continuation of application Serial No. 792,851, filed December 19, 1947, now abandoned, for Hydrocarbon Synthesis.

The present invention relates to catalytic conversions and improved catalysts therefor. More particularly, the invention is concerned with improved iron-type catalysts for the catalytic synthesis of normally liquid hydrocarbons and oxygenated compounds from C0 and H2.

Iron-type catalysts are normally employed in the synthesis of hydrocarbons at relatively high temperatures of about 450-800 F. and relatively high pressures of about 3-100 atmospheres abs. or higher, to obtain predominantly unsaturated and oxygenated products from which motor fuels with high octane ratings may be re covered.

The extreme temperature sensivity and relatively rapid catalysts deactivation of the hydrocarbon synthesis have led, in recent years, to various attempts and proposals to employ the so-called fluid catalyst technique wherein the synthesis gas is contacted with a dense turbulent bed of finely divided catalysts fluidized by the gaseous reactants and products. This technique permits catalyst replacement without interruption of the process and greatly improved temperature control. However, the adaptation of the hydrocarbon synthesis to the fluid catalyst technique has encountered serious difficulties, particularly when iron-type catalysts are used.

Application of the fluid technique requires ease of fluidization and attrition resistance in addition to the conventional characteristics determining catalyst activity, such as total desired yield and active catalyst life. It is also desirable that the catalyst be active in the temperature range above 600 F. and still be highly selective to C4+ hydrocarbons, since under these conditions high octane motor fuels are obtained. None of the prior art iron-type catalysts complies satisfactorily with all of these requirements.

Iron catalysts are usually prepared by the reduction of various natural or synthetic iron oxides or by the decomposition of iron carbonyls, the catalytic activity being on hanced by the addition of such promoters as various compounds of alkali metals or the oxides of chromium, zinc, aluminum, magnesium, manganese, the rare earth metals and others in small amounts of about 1-10%. While, some of these catalysts exhibit excellent activity characteristics they are usually deficient with respect to ease of fluidization, and/ or attrition resistance, particularly when used in commercial runs of several hundred hours duration. Even most fluidized catalysts obtained from sintered iron, which have been found to exhibit excellent fiuidization and attrition characteristics, show signs of disintegration in long run operation.

This general lack of mechanical resistance or steady decrease of mechanical strength during operation has. been found to be closely connected to a high rateof carbon deposition on the catalyst, encountered'at the conditions required by the synthesis using iron catalysts. The cat- 2,729,664 Patented Jan. 3, 1956 deposition, are a need strongly felt in the synthesis art.

Many attempts have been made to improve the disintegration resistance of this type of catalyst by varying the methods of preparation and/ or the character and proportions of addition agents. While these attempts have led, in isolated cases, to certain improvements these were the result of hit andmiss experimentation. Prior to the present invention, no generally applicable rules or means had been found which would permit to predict and prepare, with, any measure of certainty, from a wide variety of starting materials and largely independent of the method of preparation used, a loW-carbonizing, highly disintegration-resistant iron-type catalyst having satisfactory catalytic properties. The present invention fills this serious gap in the hydrocarbon synthesis art.

It is, therefore, the principal object of the present invention to provide improved iron-type catalysts for the catalytic synthesis of hydrocarbons from C0 and H2.

It is a further object of this invention to improve the hydrocarbon synthesis process by making available a Wide variety of iron-type catalysts of satisfactory activity and selectivity having desirable disintegration and carbon forming tendencies.

A more specific object of the invention is to improve the hydrocarbon synthesis process employing the fluid catalyst technique by making available a wide variety of iron-type catalysts of satisfactory activity and selectivity having low disintegration and carbon forming tendencies.

A still further object of the invention is to provide a new method by which iron-type synthesis catalysts having low carbon forming and disintegration tendencies may be selected with a high measure of certainty.

Other and further objects and advantages of the invention will appear hereinafter.

In accordance with the present invention, the carbon forming and disintegration tendencies of iron-type hydrocarbon synthesis catalysts may be controlled, quite generally, by combining the catalyst components so as to form a composite which will either prevent or permit substantial diffusion of carbide bonds, i. e. Fe-C bonds, from the surface into the lattice of the body of the catalyst, depending on the degree of catalyst carbonization and disintegration desired. When catalysts of low carbonization and disintegration resistance are desired, the catalyst components should be combined to form composites which will substantially prevent such diffusion of carbide bonds, while composites permitting such diifusion to a substantial degree represent strongly coking and readily disintegrating synthesis catalysts.

It has been found that the diffusion of carbide bonds into the lattice of the catalyst body and with it the carbon forming tendencies of iron-type catalysts may be con- I trolled in three different ways, namely by:

These three embodiments of the invention and their proper application will be best understood from the more detailed description hereinafter.

The carbon-forming tendency of a catalyst may be expressed as carbon selectivity, i. e. the mols of carbon monoxide converted to carbon on the catalyst (exclusive of wax) per 100 mols of CO converted in the hydrocarbon synthesis. The carbon combined as an iron carbide is also included in this definition. Since the catalyst age, defined in terms of cubic feed of CO converted per pound of catalyst, has a marked eifect on carbon selectivity, the carbon selectivities are directly comparable only at the same catalyst age. As a first approximation, this may be done by expressing the carbon-forming tendencies of a catalyst as a percentage of the carbon selectivity of a reference catalyst at the same age. This procedure is followed in the following description wherein all carbon data are expressed as carbon selectivity, percent of reference.

The carbon-forming tendency of a catalyst depends in part upon such operating variables as partial pressure of hydrogen, conversion level, etc. It is necessary, therefore, in comparing the effect of promoters, crystal structure, etc. upon carbon-forming tendencies of catalysts, to use comparable test conditions for all catalysts. This fact has been taken into consideration in the tabulation of data given below.

(A) COMBINING THE IRON BASE WITH A PRO- MOTER OF A CERTAIN WELL DEFINED CRYSTAL STRUCTURE Catalysts with very high carbon-forming tendencies (carbon selectivity, percent of reference, greater than about 70% under the experimental conditions described below) may be made by combining iron with a non-oxide promoter having a face-centered type of cubic crystal lattice with a lattice constant smaller than about 5.55 A. Examples of promoters that may be used are: KF, LiBr, LiCl, LiF, NaF, etc. The quantitative relationship between carbon selectivity and lattice constant is shown in the specific examples given below. Belonging to this group of high carbon formers are also such compounds as AgCl, AgF, etc. In addition, this group contains promoters of the type CaFz, etc.

Catalysts with high carbon-forming tendencies may also be made by combining iron with an oxide promoter having a face-centered type of cubic crystal lattice with a lattice constant smaller than about 5.0 A. Examples of promoters that may be used are: CaO, CdO, MgO, MnO, etc. Belonging to this group are also such promoters as CoO, NiO, TiO. In addition, such promoters as LizO, etc., belong to this group.

Catalysts with low carbon-forming tendencies (carbon selectivity, percent of reference, less than about 50% under the experimental conditions described below) may be made by combining iron with a promoter having a facecentered type of cubic crystal lattice with a lattice con stant larger than about 5.8 A. Examples of this type of promoters are: KBr, CsF, KCl, KF, LiI, RbBr, RbCl, RbI, and others. This group also contains promoters of the type SrClz, KCN, etc.

Among the face-centered type promoters is a number of materials having lattice constants between about 5.6 and 5.8. This group includes NaCl, RbF, etc. Catalysts made with these promoters show intermediate carbonforming tendencies. In certain instances low carbon-forming tendencies may be obtained, but the catalysts are quite sensitive to operating conditions and moderate changes may increase carbon formation to a high value.

Catalysts with low carbon-forming tendencies may be made by combining iron with a promoter having a bodycentered type of cubic crystal lattice. Examples of such promoters are: CsBr, CsI, and others. For the same purpose, iron may be combined with a promoter support having an hexagonal or triclinic type of crystal lattice.

4 Examples of promoters falling into this group are: ZnO, BeO, A1203, TiaOs, CuO, and others. Also combination of iron with a promoter having an aragonite or scheelite type of crystal lattice leads to catalysts with low carbonforming tendencies. Examples of promoters of this type are: BaCOa, SrCOa, BaMoOt, BaWOt, etc.

(B) COMBINING IRON HAVING A CERTAIN WELL DEFINED CRYSTAL STRUCTURE WITH THE OTHER CATALYST COMPONENTS Catalysts with relatively high carbon-forming tendencies may be made by combining suitable catalyst addition agents with iron compounds which, upon reduction, will give iron with a surface at least a portion of which has a face-centered lattice structure. Examples of iron compounds of this type are: FeO and F6304, gamma FezOs also falls into this category.

Catalysts with low carbon-forming tendencies may be made by combining suitable catalyst additions with iron compounds which, upon reduction, will give iron having an exclusively body-centered crystal lattice. Examples of iron compounds falling into this group are: Alpha- FezOa (Williams red iron oxide, Hanna hematite, specular hematite), iron carbonyl, and others.

Catalysts with low carbon-forming tendencies may also be made by alloying with iron materials which, upon reduction, form body-centered lattice structures with iron. Examples of such alloying materials are: chromium, columbium, molybdenum, uranium, vanadium, tungsten (alpha form). Catalysts with low carbon-forming tendencies may also be obtained by combining iron with supports having hexagonal, aragonite, scheelite, etc. crystal structures. Examples of such supports are: A1203, BaCOs, SrCOa, etc.

Alloying iron with materials which form with iron intermetallic compounds having a cubic body-centered structure will likewise lead to catalysts with low carbonforming tendencies. Examples of metals which form such compounds with iron are: Aluminum, silicon, zinc, etc.

(C) COMBINING IRON WITH OTHER ELEMENTS TO FORM ALLOYS AND INTERMETALLIC COM- POUNDS WHICH PREVENT DIFFUSION OF THE CARBON BONDS INTO THE CATALYST Catalysts falling within this broad class of materials have low carbon-forming tendencies. Examples of elements forming with iron compounds of the type specified are those which are capable of forming intermetallic compounds having a cubic body-centered crystal structure or any other structure preventing the formation or diffusion of carbon bonds, such as silicon, aluminum, zinc, etc. Chromium, vanadium, and other alloying elements which affect the stability of the carbide and the rate of difiusion of the carbon into the lattice are likewise suitable for this purpose.

Combinations of the methods described under A, B and C may be employed. For example, Fe-Cr-Si alloys, doubly promoted composites, such as ZnO-FezOs-KzCOs, CuO-FezOz-AlzOg, etc. yield active catalysts having low carbon-forming tendencies.

While the present invention is not to be limited to any specific theory or reaction mechanism and the reasons underlying the influence of the crystal structures and composites described above on carbide bond diffusion and carbon formation are not yet fully understood, the phenomena observed by the inventor may be reasonably well explained as follows.

One of the primary steps in the formation of carbon on an iron-type synthesis catalyst is believed to be the formation of Fe-C bonds on the surface of the catalyst. This may occur by reaction of carbon monoxide with the surface, probably after the chemisorption of CO by the surface. These F e-C bonds eventually result in the formation of iron carbide (considered here as FezC). The formation of the carbide bonds occurs with difficulty on a body-centered iron, i. e. the iron crystal structure stableat room temperature. However, the carbide may form readily from face-centered ire-n, i. e. the form that is normally stable above 1335 F. Upon reduction of a catalyst, such as mo; in the form of Williams red oxide or Hanna hematite, a body-centered iron is formed on the 6 Fe-C bond or perhaps of the iron carbide itself takes place.

However, as has just been stated, the crystal structure of the body of the catalyst is not affected by the structure or" the surface. The carbide carbon consequently has to force its way into the body of the crystalline catalyst. This difiusion into the crystal lattice may cause lattice surface of this catalyst. Consequently, the iron carbide bonds form with diiiiculty under synthesis conditions. The carbide bonds that do form, do so probably by either causing local changes in the structure of the catalyst, or 10 by forming slowly at such activated centers as incompleted lattices, points of discontinuity in lattices, such as impurities on the surface, points of strain, etc. But whatever the cause of the slow formation of Fe-C bonds, a high concentration of carbide (Fe-C bonds) does not build upv rapidly and consequently diffusion of the carbide bonds into the lattice is slow. This results in a low rate of carbon formation as will appear moreclearly hereinafter.

When considering a crystal bounded bya surface, the distribution of the atoms or ions in the main body of the crystal far from the surface is not influenced by the presence of the surface and may be considered as being described adequately by the data obtainable by X-ray and other similar methods of study. The distribution of the atoms near the surface can, however, be different from the internal atomic distribution. The type of difference depends upon the kind of crystal, the orientation of the surface in respect to the planes of the crystal, and the kinds of adsorbed atoms or ions. In the case of pure red iron oxide, few, if any, atoms or ions are adsorbed on the surface and, except for lattice imperfections and strains, the structure of the surface is not too different from that of the bulk of the catalyst. If, on the other hand, a promoter TABLE Ir-EFFECT OF LATTICE CO changes to take place.

This in turn can cause cleavage of the crystal along its various lines of cleavage, including those along crystalline interfaces.

On the other hand,

since there is little, if any, CO in the body of the crystal, the carbide is thermodynamically unstable and decomposes to form iron and carbon.

This decomposition of the carbide causes-an expansion to take place, with a con-v sequent rupture of the lattice.

Thus, a face-centered promoter results in a high rate of Fe-C bond formation,

resulting in rapid diffusion of the carbide carbon into the lattice, which, in turn, results in the rupture of the lattice, catalyst disintegration and coke deposition.

The catalysts of the present invention may be prepared by combining the proper catalyst suitable method of coprecipitation, iron component components by any precipitation of the on a suitable precipitated support, im-

pregnation or mechanical mixing, known per se in the art of catalyst manufacture, followed by reduction.

The invention Will be further illustrated by th ing specific examples.

Example I e follow- The effect of the lattice constant of face-centered promoters or supports on the carbon-forming tendencies the, experimental of iron type catalyst is demonstrated by data tabulated below.

NSTANT OF FACE-CENTERED TYPE PROMOTOR OR SUPPORT SMALL Crystal r- Temp, F. Promoter Structure ag? Percent carllaon Catalyst or Supof PIO scant Conv cJm. Perc'nt PM g f g g (A) Red. Syn. of Ref.

MgO.Fe O3 f MgO 0i, 4. 20 900 550 as 165 95 1\'IDO.F0203 MnO 0%, 4.44 900 563 94 155 Li2Q.FEgO3 Luo 0?, 4.61 900 650 100 80 FezOs+1% KF KF 0%, 5.33 1,000 600 94 203 95 LARGE Fel0+r% CsF CsF 0 6.01 900 610 97 209 27 FegOs+1% KCl Kor 0; 6.28 900 570 98 183 39 Fe2Os+1.7% KBr 7 KB! 0 6.58 900 580 98 17s 41 Fermi-1.0% Ker -KBr 0'; 6. 5a 900 560 97 22 FeaOs+2.4% KI KI 02, 7.05 900 555 97 209 45 The space-group symbols such as Oitfor a face-centered cubic crystal) are discussed in detail in such standard texts as Wycofi, The Structureof Crystals; Bragg,

' Crystal Structures audits Applications.

. constant of 5.3 A.

atomic Structure of Minerals; and Davey, Study of The above data show that although CsF and KP have very similar chemical properties and would be expec ted, from an examination of the periodic table, to act in a similar manner, the CsF with a lattice constant of 6.0 A is a very much lower carbon former than KP with a lattice the As is shown by the following data, KP and Cs? promoted catalysts have similar initial activity and selectivity in the hydrocarbon synthesis reaction per se but ditier very significantly in carbon-forming tendencies.

TABLE IL-EFFEO'I F LATTICE CONSTANT TABLE IV.-EFFEOT OF ALLOYS AND INTERMETALLIO COMPO UN DS Promoter on Red Iron Oxide (F6903) CsF KF 04+ C ar bon Added Temp. Percent cc./1:n Lattice Constant of Promoter (A 6.0 5. 3 Catalyst 0 a tlvity, Temperature F.) 610 580 0 Element Syn COIN 'g g Percent 04+ Yield (cc/n1 cons.) 209 190 of Ref. Alcohol Yield (cc./m. cons). 12 17 Cat. Age (CF 00 conv.l# cat.) 155 211 0 Sci. (Percent of Ref.) 27 106 52Fe-48Si Silicon 650 97 183 2 :rFe-y Or Ohromium 650 87-93 146-166 18 Example II The effect of the type of iron compound used for reduction on the carbon-forming tendencies of iron-type catalysts is illustrated by the data given in Table III below.

TABLE Ill-EFFECT OF IRON COMPOUND USED FOR REDUCTION 0 Carbon 0 1 Temp. F. Percent eejmf $325,

ompound Crysta Structure Red. syn Con H+OO ermit Cons of Ref.

0: F8203 Williams Red Oxide Hexagonal 900 560 96 125 4 Hanna Hematite... do 900 590 96 132 4 F8304 F6304 cubic, FeO face- 900 580 97 121 41 centered cubic.

It may be seen that catalysts obtained from iron having the crystal structure prescribed by the present invention have extremely low carbon-forming tendencies.

Example 111 The following table illustrates the effect of alloys and intermetallic compounds preventing carbide bond diffusion into the catalyst body.

The above data show that substantially no carbon is formed on catalysts of this type.

Example IV The effects of promoters or supports having a nonfacecentered cubic structure on the carbon-forming tendencies of iron type synthesis catalysts are summarized below in Table V. The crystal structure of these promoters or supports is given in Table VI.

TABLE V.-EFFECT OF PROMO'IERS AND SUPPORTS TERED CUBIC STRUCTURE WITH A NONFAOE-OEN- Temp, F. Oiarlam re ec vwe arser a e a Red. Syn. Bet

SOBaOOJ-2OFeCOQ 900 630-650 96 211 32 SOCaOOa-ZOFeC O3 900 650 96 205 16 ZnO.Fe2Oa 990 560 157 8 SOZnO-ZOFegOa Z O 900 575-650 94-6 148 10 99 (ZnO-20FezO3)+1K2COa- 900 620-650 95 200 28 FeOAhO; 900 612 99 166 16 Be0.FezO 900 560 91 179 33 900 615 95 210 28 OuO-i-AlzOa.-- 900 555 94 129 3 CuO-l-Zn0 900 650 98 12 C 990 530 94 190 20 900 550 93 30 900 600 95 168 45 TABLE VL-CRYSTAL STRUCTURE OF VARIOUS PROMOTERS OR SUPPORTS Promoter or Support Crystal Structure or System 8 323; Remarks BaOO; Rhombic V}: CaCOa: m (Aragonite) V (Calcite) Rhombohedral 13g,

ZnO hexagonal cg, BeO .-do 0g.

OuO monoclinlc (a) hexagonal C cubic 0}, mo, -110 0}, Other forms of s10, have hexagonal and rhombic forms. CsBr do 0}, K2003 Similar to LlzCOa which is Rel; Gmelins Handbuch der monoelinlc. Anorganlschen Ohemie System, Nos. 20 and 22.

It will be seen that the presence of a nonface-centered type cubic crystal structure quite generally depresses carbon formation to a fraction of the carbon selectivity of the reference catalyst.

Typical methods of preparing and testing (in fixed bed operation) representatives of the various classes of catalysts selected and combined in accordance with the present example are given below.

Example V (1) Face-centered promoter with large lattice constant Fe2O3+1% CsF Synthesis temperature, F 610 CO conversion, percent 97 C4+ yield (cc./m. feed consumed) 209 Catalyst age (cu. ft. CO converted/lb. of catalyst) 155 Carbon selectivity (percent of reference) 27 (2) Hexagonal and triclinic composites (A) BeO.Fe2O3 71.9 gms. of BeO were added to a solution containing 203 cc. of concentrated HNOs in 500 cc. of distilled water. To this mixture was added a solution containing 1313 gms. of ferric nitrate in 3 liters of water. The final solution was made up with distilled water to 6 liters. This solution was added simultaneously With a solution containing 533 gms. of NaOH in 6 liters of water to a crock containing 6 liters of water. The pH was maintained at 9. The precipitate was filtered, washed, reslurried, refiltered and rewashed. After drying and then calcining for 3 hours at 1600 F., the catalyst was reduced and tested as described above.

Synthesis temperature, F 560 CO conversion, percent 91 01+ yield (cc./m. feed consumed) 179 Carbon selectivity (percent of reference) 33 (B) 80 ZnO20 FezOs A solution of 1016 gms. of Fe(NO3)3.9H2O in 2 liters of water was added very slowly to a slurry of 1106 gms. of ZnO in 3 liters of water. The mixture was stirred until all of the iron had been precipitated. After filtering, washing, reslurrying, refiltering and rewashing, the precipitate was dried at 250 F. and then calcined for 3 hours at 850 F.

The catalyst was reduced at 900 F. with H2 at 1 atm. pressure and 1000 v./v.hr. and then tested with a feed gas having a ratio of H2/CO=l at 250 p. s. i. g. pressure and 200 v./v./hr.

Synthesis temperature, F 575-650 The effect of K2CO3 promoter on this supported catalyst may be seen from the following data:

(C) 99 80Zno-20Fez0s) +lK2COa Half of the above washed filter cake was mixed in a paste with gms. of KzCOz. The catalyst was dried and then calcined at 850 F. for 3 hours. After reduc- 10 tion at 900 F. with H2 at 1 atm. pressure and 1000 v-./v./hr., the catalyst was tested with a feed gas having a ratio of H2/CO=1 at 250 p. s. i. g. pressure and 200 v./v./hr.

(3) Aragonite or scheelite type composites 80BaCO3-20F6CO3 A solution of 344 gms. of FeClzAHzO in 2 liters of water was added slowly to a slurry of 1141 gms. of BaCOs in 3 liters of water. Contact with air was kept at a minimum during these steps. After stirring for 1 hour, an additional 149 guns. of ferrous chloride, dissolved in 600 cc. of Water were added, and then, while stirring 285 gms. of ammonium carbonate, dissolved in 1 liter of water, were added. The mixture was stirred for 1 hour, the precipitate was then permitted to settle and was washed free of chloride ion by decantation. The precipitate was dried at 250 F. in a stream of C02.

The catalyst was reduced at 900 F. with 1 atm. Hz at 1000 v./v./hr. and then tested with a feed gas having a ratio of H2/CO=1 at 250 p. s. i. g. pressure and 200 v./v./hr.

Carbon selectivity (percent of reference) 32 Percent CO3: after use -22 Theoretical for 1321003 -27 1 Agreement within experimental error.

While the above experimental data were obtained in fixed bed operation, the relative comparisons hold for fluid operation, even though the higher gas throughputs, high recycle ratios and high catalyst turbulence typical for fluid operation, quite generally, cause a slight decrease of conversion and liquid product yields and an appreciable increase of carbon formation and catalyst disintegration. It follows that the catalysts of the invention, as a result of their greatly reduced carbonization and disintegration tendency and their superior liquid product selectivities even at high temperatures coupled with long catalyst life, are particularly useful for fluid catalyst operation and in this respect greatly superior to other catalysts of the iron type. Catalysts, in accordance with the invention, suitable for fluid operation may be prepared substantially as outlined in the above examples and sized to particle sizes of about 20-150 microns, preferably 50-l00 microns. The conditions of fluid synthesis operation are well known in the art and need not be specified here in any great detail for a proper understanding of the invention by those skilled in the art. Briefly, these conditions may include catalyst particle sizes of 5200 microns, superficial linear gas velocities of about 0.1-3 ft./sec., bed densities of about 10-120 lbs. per cu. ft., HzzCO ratios of about 0.5-3, gas recycle ratios of about 0-5, temperatures of about 550-750 F., and pressures of about 150-650 lbs. per sq. in.

While the foregoing description and exemplary operations have served to illustrate specific applications and results of the invention, other modifications obvious to those skilled in the art are within the scope of the invention. Only such limitations should be imposed on the invention as are indicated in the appended claims.

What is claimed is:

A method of synthesizing normally liquid hydrocarbons and oxygenated hydrocarbons by a reaction between carbon monoxide and hydrogen which comprises contacting the said carbon monoxide and hydrogen at synthesis conditions of temperature, pressure and contact time with a bed of fluidized catalyst consisting essentially of a reduced alpha ferric oxide catalyst associated with approximately 1 weight per cent of caesium fluoride, based on the total Weight of the catalyst, and recovering from the reaction a product containing normally liquid hydrocarbons and oxygenated hydrocarbons.

References Cited in the file of this patent UNITED STATES PATENTS Michael et a1. Dec. 12, 1944 Eggertsen et a1. Jan. 21, 1947 Hawk et al Sept. 14, 1948 Schiller Oct. 10, 1950 Segura May 8, 1951 FOREIGN PATENTS Great Britain Nov. 7, 1928 

